CN109752663A - A kind of measurement method of the internal resistance of cell - Google Patents
A kind of measurement method of the internal resistance of cell Download PDFInfo
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- CN109752663A CN109752663A CN201711058232.2A CN201711058232A CN109752663A CN 109752663 A CN109752663 A CN 109752663A CN 201711058232 A CN201711058232 A CN 201711058232A CN 109752663 A CN109752663 A CN 109752663A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/389—Measuring internal impedance, internal conductance or related variables
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/367—Software therefor, e.g. for battery testing using modelling or look-up tables
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/382—Arrangements for monitoring battery or accumulator variables, e.g. SoC
- G01R31/3835—Arrangements for monitoring battery or accumulator variables, e.g. SoC involving only voltage measurements
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
- H01M10/486—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte for measuring temperature
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R27/00—Arrangements for measuring resistance, reactance, impedance, or electric characteristics derived therefrom
- G01R27/02—Measuring real or complex resistance, reactance, impedance, or other two-pole characteristics derived therefrom, e.g. time constant
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The present invention provides a kind of measurement methods of internal resistance of cell, after carrying out charge or discharge operation to tested battery with preset electric current, voltage value when recording charge or discharge cut-off to voltage stabilization, is calculated three kinds of polarization (i.e. ohm/ohmic polarization, activation polarization and concentration polarization) corresponding internal resistances of battery.Present invention utilizes the difference that above-mentioned three kinds polarization are restored to the characteristic time magnitude of new equilibrium state after charge or discharge, these three polarized values are extracted to by the confining method of clear and definite and distinguish and be used for the calculating of respectively corresponding internal resistance.By showing method proposed by the present invention confidence level with higher and very strong practicability with the comparison of other related experiments and the verifying of multiple embodiments.
Description
Technical field
The present invention relates to a kind of measurement methods of internal resistance of cell.
Background technique
The internal resistance of battery has very big shadow to the release of battery capacity and high-power charge-discharge performance and internal heat production
It rings.Therefore when designing battery, internal resistance is a parameter for needing emphasis to detect.And there are many factor for influencing internal resistance size, than
Such as the electric conductivity of pole piece, electrolyte, collector itself, chemical property and charge between electrode activity thing and electrolyte
Transmission performance etc. in the solid phase and the liquid phase.It, will if the method that internal resistance caused by these different reasons is distinguished can be found
Optimization, the analysis of failure mechanism etc. of battery core and module design are played an important role.
Measure there are mainly two types of most common methods the internal resistance of cell at present: one is direct current methods, and one is alternating current methods.
Direct current method survey internal resistance common practice be: under some state-of-charge (SOC, State of Charge) of battery into
The constant-current discharge of row certain time (can be 5s, 10s, 20s etc.), record electric discharge before voltage (being at this time open-circuit voltage) and
Final discharging voltage (minimum point for typically referring to discharge voltage), and by the difference of the two voltages (after usually the former subtracts
Person) divided by the electric current of constant-current discharge, value is counted as the DC internal resistance of battery.Such as patent application CN 103529301A.Second
Kind measurement method is to survey internal resistance using the rise (or falling after rise) of voltage after electric discharge (or charging).These methods are mainly logical
Cross voltage value and the electric discharge of first point that measurement battery is measured when stopping electric discharge (or charging) voltage recovery (or falling after rise) afterwards
Electric current before difference between voltage value at the end of (or charging) terminates divided by electric discharge (or charging) again calculates ohm of battery
Internal resistance.These methods are the problem is that first point of voltage recovery (or falling after rise) depends on after to electric discharge (or charging)
The resolution ratio of measuring instrument and there is no a clear and definite criterion, so obtained result is more casual, and not
It can reflect actual physical meaning.Actually since the characteristic time (also referred to as time constant) of ohmic polarization (or ohmic polarization) is non-
It is often short, i.e., generally in the order of magnitude of 10 microseconds, by basis described in above-mentioned second of DC measurement method being previously mentioned
The point that first point of the voltage recovery (or falling after rise) that measuring instrument resolution ratio obtains sees ohmic polarization disappearance as has very big
Randomness and inaccuracy.And even if differing 0.1 second, error is also huge for the characteristic time of ohmic polarization
Big.Additionally due to there are electric double layers for electrode surface.In electric discharge (or charging) initial period that electric current stops, voltage is not to stand
It carves (or falling after rise), but has a slow change procedure (needing to fill electric double layer or discharged).Based on above-mentioned original
Cause is only knot that is infeasible, obtaining come the disappearance for judging ohmic polarization by first point of selection voltage recovery (or falling after rise)
Fruit is also inaccuracy.
Usually, it according to the different reasons that polarization generates when charge and discharge, can simply be divided into three classes: ohmic polarization,
Activation polarization and concentration polarization.Another defect that direct current method described above surveys internal resistance is that it can not be different former by these
It polarizes and distinguishes because caused by.
Alternating current method is surveyed there are two types of the usual ways of internal resistance.One is using AC internal Resistance measuring instrument directly to measure, generally frequently
Rate is selected in 1KHz or so.But this method can only measure ohmic internal resistance, and for electric charge transfer internal resistance (by electrochemistry pole
Change cause) and spread internal resistance (being caused by concentration polarization) can not measure.Another method is also to be electrification using ac impedance spectroscopy
It learns impedance spectrum (Electrochemical Impedance Spectroscopy, EIS).Battery can be measured close with EIS
Ohmic internal resistance and electric charge transfer internal resistance under equilibrium state, but diffusion internal resistance can not be measured.Because with EIS method test cross flow resistance
Anti- time spectrum requires voltage disturbance amplitude very small (generally in 5mV or so), so will be unable to measure battery in this way in reality
Above-mentioned two internal resistance value of (actual current is far longer than EIS and measures permitted range) in the use of border.
Summary of the invention
It is an object of the present invention to provide a kind of measurement methods of internal resistance of cell, comprising:
A. battery is provided, control battery temperature reaches test temperature；
B. constant-current discharge is carried out to battery using predetermined current I or ended after the one preset time of charging, record is from putting
The cell voltage of electricity or charge cutoff moment to voltage when steady；
It detects battery discharge or the battery voltage value at charge cutoff moment is V1, the cell voltage after the disappearance of ohm overpotential
Value is V2,
C. according to formula Ro=| V2-V1 |/I calculates ohmic internal resistance Ro.
In above-mentioned test method, control battery temperature reaches test temperature, and can adjust test environment temperature first extremely needs
The temperature (can be room temperature or the operating temperature that other batteries allow) wanted, then places battery in this context until its temperature
Degree reaches balance, i.e., consistent with environment temperature and no longer change, and error can permit within ± 2 DEG C.
In the present invention, constant-current charge or electric discharge can be carried out to battery using cell tester, use high-speed data acquisition
Instrument is acquired the voltage of battery.Battery to be tested is connected to cell tester and (its resolution of high-speed data acquisition instrument
Rate is preferably acquisition 10 per second6A data point or more) on, under the test environment under no load stand a period of time until
Its voltage reaches balance, this time can be 0~2h or longer according to the actual situation, then carries out constant-current discharge or charging.
Specific test connection schematic diagram is shown in Fig. 1.
After electric discharge (or charging) current cut-off, the battery voltage value after record ohm overpotential disappears is V2, that is, is being discharged
Since current load loses after (or charging) cut-off, the battery voltage value after the disappearance of ohm overpotential.When the feature of ohmic polarization
Between magnitude in 1 microsecond between 1 millisecond.The effect due to inside battery solid liquid interface electric double layer, voltage are found in actual measurement
Rise (or fall after rise) be a slow process, have an apparent platform, platform institute after this slow process
Corresponding voltage is V2.The platform electricity of first platform of the value of the i.e. described V2 for voltage recovery after V1 or after falling after rise
Pressure.Schematic diagram difference under electric discharge and charging situation is referring to figs. 2 and 3.
By using AC electrical method to survey the ohmic internal resistance of battery in the same state and the contrast verification of the value value
The accuracy of method.It should be noted that the characteristic time of activation polarization and concentration polarization is all far longer than ohmic polarization
Characteristic time, so value here assumes that the variation of activation polarization and concentration polarization can within this period from V1 to V2
To ignore.
It is another object of the present invention to provide a kind of measurement methods of internal resistance of cell, comprising:
A. battery is provided, control battery temperature reaches test temperature；
B. constant-current discharge is carried out to battery using predetermined current I or ended after the one preset time of charging, record is from putting
The cell voltage of electricity or charge cutoff moment to voltage when steady；
Detecting the battery voltage value after ohm overpotential disappears is V2, after ohm overpotential and electrochemistry overpotential disappear
Battery voltage value is V3,
C. according to formula Rct=| V3-V2 |/I calculated charge shifts internal resistance.
Battery voltage value after ohm overpotential and electrochemistry overpotential disappear is V3, electricity of the data point of V3 after V1
Within the scope of the characteristic time of chemical polarization (characteristic time magnitude is between 1 millisecond to 1 second).The present invention by following formula come
Determine V3 data point, i.e., when voltage is less than preset value C1 relative to the ratio between changing value of time and the moment voltage value after V2
When point:
|dV/dt|/V<C1
It should be noted that common, the value of C1 can choose in 0.001s value to C1-1To 0.5s-1Between.
Large error is had between the Rct and true value finally calculated if C1 value is excessive, is needed again if C1 value is too small
Consider the influence caused by changed by concentration polarization to collected data.Value by many experiments verifying C1 exists
0.01s-1To 0.2s-1Between when not only can guarantee the accuracy of calculated result but also can effectively reduce concentration polarization variation bring
It influences.
In another embodiment of the present invention, the V3 is the changing value and the moment voltage when voltage relative to the time
The voltage value of battery when the ratio between value is less than preset value C1, and the value of C1 is in 0.01s-1To 0.2s-1Between.
The value of C1 is in 0.01s-1To 0.2s-1Between when can effectively reduce concentration polarization variation bring influence, and
It ensure that calculated result is more accurate.
It need to be noted that be a bit because when the characteristic time of concentration polarization is far longer than the feature of activation polarization
Between, so value here assumes that the variation of concentration polarization can be ignored within this period from V2 to V3.It causes
Error within tolerance interval.
It is another object of the present invention to provide a kind of measurement methods of internal resistance of cell, comprising:
A. battery is provided, control battery temperature reaches test temperature；
B. constant-current discharge is carried out to battery using predetermined current I or ended after the one preset time of charging, record is from putting
The cell voltage of electricity or charge cutoff moment to voltage when steady；
It detects ohm overpotential and disappears the battery voltage value after disappearing with electrochemistry overpotential for V3, ohm overpotential, electricity
Battery voltage value after chemical overpotential and concentration overpotential all disappear is V4,
C. according to formula Rd=| V4-V3 |/I calculates diffusion internal resistance.
The value of battery voltage value V4 after ohm overpotential, electrochemistry overpotential and concentration overpotential whole disappearance needs
After battery starts against new balance, i.e., cell voltage reach steady after voltage value.The Selecting time of V4 is not because
It is different with battery design and different electric discharges (charging) time, it can choose at least 30 minutes.
Voltage steadily refers to that the voltage of battery keeps relative stability, and can permit ± 2% error.
In another embodiment of the present invention, the test temperature is -30 DEG C to 60 DEG C.
The operating ambient temperature of battery is general between -30 DEG C to 60 DEG C in practical application, this temperature range is selected to carry out
Measurement can also measure battery and exist primarily to the internal resistance of cell measured is able to reflect the practical working situation of most of battery
Internal resistance under extreme temperature (such as 60 DEG C or more).
In the present invention, SOC state to tested battery is simultaneously not construed as limiting, and when battery is in 0%SOC, can be used
Charging method carries out battery testing, when battery is in 100%SOC, can carry out battery testing using charging method.
In another embodiment of the present invention, being tested battery is 50%SOC.
In another embodiment of the present invention, being tested battery is 95%SOC.
In another embodiment of the present invention, being tested battery is 25%SOC.
In another embodiment of the present invention, any value of the predetermined current I selected from 0.1C into 30C.
In another embodiment of the present invention, any value of the predetermined current I selected from 1C into 10C.
Method of the invention is speeded after charge and discharge using difference of polarized characteristic time caused by different reasons
The time difference of each autoregression equilibrium state distinguishes in the time of Henan.Usually, ohmic polarization is mainly since electric current flows through
It is formed by polarization when Ohmic resistance on electrode system, can usually be rapidly disappeared after charge and discharge, the characteristic time is 1
Microsecond is between 1 millisecond.And activation polarization is mainly since charge transmits in electrode active material and electrolyte interface layer
The polarization of formation.Since this boundary layer is usually very thin, so the time that activation polarization after charge and discharge disappears
Shorter, its usual characteristic time is between 1 millisecond to 1 second.Concentration polarization includes concentration polarization and electrode active in electrolyte
Concentration polarization in property substance.The former characteristic time is generally between 1 second and 1000 seconds, and the characteristic time of the latter generally exists
Between 100 seconds and 10000 seconds.The present invention is restored after charge and discharge using ohmic polarization, activation polarization and concentration polarization
These three polarized values are extracted and are distinguished by the different characteristic time to new equilibrium state, accuracy with higher and very
Strong practicability.
The present invention can be suitable for the battery of not type, and can be effectively by ohmic polarization, activation polarization and dense
Difference polarization distinguishes, and is compared by the internal resistance of the battery measured with ac impedance spectroscopy (EIS) method in fc-specific test FC
The accuracy of method proposed by the present invention is demonstrated, optimization battery design, battery failure will be analyzed, inside battery core with this method
Heat production, estimation of SOC/SOH/ power limit etc. play an important role.
Detailed description of the invention
Fig. 1 is the equipment of the measurement internal resistance of cell of the embodiment of the present invention and the connection schematic diagram of tested battery；
Fig. 2 is the schematic diagram of the voltage of the measurement battery of one embodiment of the invention, electric current and time graph；
Fig. 3 is the schematic diagram of the voltage of the measurement battery of another embodiment of the present invention, electric current and time graph；
Fig. 4 is the EIS data and Equivalent Circuit Fitting curve graph of one embodiment of the invention measurement.
Specific embodiment
Embodiment 1
In the present embodiment using to key instrument equipment include computer, a Tai Xinwei cell tester (CT-4004-
5V300A-NTFA), for carrying out charge and discharge, the voltage of a high-speed data acquisition instrument detection battery, He Yitai to battery
(instrument is only used for the comparative experiments of the method for the present invention to Autolab PGSTAT302N electrochemical workstation, is not the present invention
Instrument necessary to method), other equipment are common accessory.
Measurement object is lithium ion battery A in the present embodiment, and just extremely trielement composite material, cathode are porous carbon
Material, marked capacity 10Ah are comprised the steps that
1. lithium ion battery A is connect with measuring device according to Fig. 1.
2. the temperature that lithium ion battery A is placed in thermostatic chamber, and controls lithium ion battery A is 25 DEG C.
3. its SOC is adjusted to 50% according to the marked capacity of lithium ion battery A and reaches balance (in charging and discharging currents section
It is considered that reaching balance after standing at least 1 hour after only).
4. adjustment lithium ion battery A temperature reaches 25 DEG C.
5. using the electrochemical impedance spectroscopy (EIS) of electrochemical workstation measurement lithium ion battery A.
6. adjustment lithium ion battery A temperature reaches 25 DEG C.
7. using 1C electric current to lithium ion battery A electric discharge 10s, while using cell tester and high-speed data acquisition instrument
(time step is set as 10 microseconds) recording voltage data.
8. standing 1 hour.
9. its SOC is adjusted to 50% according to the marked capacity of lithium ion battery A and reaches balance (in charging and discharging currents section
It is considered that reaching balance after standing at least 1 hour after only).
10. repeating step 6 to 9 (discharge current need to be changed to 2C, 3C, 4C, 5C and 6C in step 7) until completing all
Test.
It should be noted that in the present embodiment step 7 discharge time be set as 10s, but this value can be according to actual needs
It is adjusted.Situation is identical with this in all embodiments below, will not be illustrated one by one.
Fig. 2 is the schematic diagram of the voltage to the battery measured in the embodiment, electric current and time graph, when horizontal axis indicates
Between, it is only used for referring to, does not represent true time scale.
The lithium-ion electric that the method is measured and is calculated through the invention under table 1 lists discharge current from 1C to 6C
The ohmic internal resistance value (Ro) of pond A is calculated according to formula Ro=(V2-V1)/I, detects the cell voltage of battery discharge cut-off time
Value is V1, the platform voltage of first platform after the value of V2 is V1 after voltage recovery.The ohmic internal resistance value obtained from table 1
It can be seen that its value may be considered substantially not with discharge current change and change, this is the characteristic for meeting ohmic internal resistance itself
's.
In addition Fig. 4 shows the EIS curve (band point curve in Fig. 4) obtained by electrochemical workstation measurement and uses
The curve that equivalent circuit is fitted it (without point curve in Fig. 4).From in figure in the equivalent circuit diagram of the upper right corner each element fitting
The ohmic internal resistance value for being worth available lithium ion battery A is Ro=1.00m Ω, very with ohmic internal resistance Ro value obtained in table 1
It is close.It is very high for the accuracy for measuring and calculating ohmic internal resistance that this also demonstrates the present invention.
1. lithium ion battery A ohmic internal resistance of table
Table 2. list discharge current respectively from 1C to 6C under the method is measured and is calculated through the invention lithium
The electric charge transfer internal resistance value (Rct) of ion battery A is calculated according to formula Rct=(V3-V2)/I, and the data point of V3 is by following public affairs
Formula is determining, i.e. the point when voltage is less than preset value C1 relative to the ratio between changing value of time and the moment voltage value: | dV/dt
|/V < C1, the value of C1 is 0.05s in the present embodiment-1。
If the available fitting a straight line of value of the Rct being fitted with straight line in table 2 under different discharge currents
Equation are as follows: y=-0.013x+3.5.Wherein y is Rct, and x is discharge current (unit A).From fit equation it can be concluded that working as
When electric current x=0, Rct value is 3.5m Ω.
Separately it is by the electric charge transfer internal resistance value that Fig. 4 electrical equivalent is fitted the lithium ion battery A that EIS data obtains
The value 3.5m Ω of 3.75m Ω (referring to fig. 4 in Rct value), the Rct obtained with above-mentioned fit equation in electric current=0 is very close,
This is also demonstrated be the method for the present invention when applying electric current close to 0 with the electric charge transfer internal resistance that EIS method measurement obtains one
Special case, while the method for the present invention is demonstrated with strong validity and high accuracy.
2. lithium ion battery A electric charge transfer internal resistance of table
The lithium ion that the method is measured and is calculated through the invention under table 3. lists discharge current from 1C to 6C
The diffusion internal resistance value (Rd) of battery A is calculated according to formula Rd=(V4-V3)/I, and the data point of V4 is that cell voltage reaches steady
Voltage value afterwards.
Because can not be compared here by the diffusion internal resistance value for the lithium ion battery A that EIS is directly measured, this
It is also the advantage that the present invention compares EIS.
3. lithium ion battery A of table spreads internal resistance
Embodiment 2
In the present embodiment using to key instrument equipment include computer, a Tai Xinwei cell tester (CT-4004-
5V300A-NTFA), for carrying out charge and discharge, the voltage of a high-speed data acquisition instrument detection battery to battery, other equipment are
Common accessory.
Measurement object is lithium ion battery B in the present embodiment, and just extremely trielement composite material, cathode are porous carbon
Material, capacity 10Ah are comprised the steps that
1. lithium ion battery B is connect with measuring device according to Fig. 1.
2. the temperature that lithium ion battery B is placed in thermostatic chamber, and controls lithium ion battery B is 25 DEG C.
3. its SOC is adjusted to 50% according to the marked capacity of lithium ion battery B and reaches balance (in charging and discharging currents section
It is considered that reaching balance after standing at least 1 hour after only).
4. adjustment lithium ion battery B temperature reaches 25 DEG C.
5. lithium ion battery B is charged 10s with 1C electric current, at the same using cell tester and high-speed data acquisition instrument (when
Between step-length be set as 10 microseconds) recording voltage data.
6. standing 1 hour.
7. its SOC is adjusted to 50% according to the marked capacity of lithium ion battery B and reaches balance (in charging and discharging currents section
It is considered that reaching balance after standing at least 1 hour after only).
8. repeating step 4 to 7 (charging current need to be changed to 2C, 4C etc. in steps of 5) until completing all tests.
Fig. 3 is the schematic diagram of the voltage to the battery measured in the embodiment, electric current and time graph, when horizontal axis indicates
Between, it is only used for referring to, does not represent true time scale.
Table 4. lists in the case that charging current is 1C, 2C, 4C, 6C respectively, and the method measurement is simultaneously through the invention
The ohmic internal resistance value (Ro) for the lithium ion battery B being calculated is calculated according to formula Ro=(V1-V2)/I, detects battery discharge
The battery voltage value of cut-off time is V1, the platform voltage of first platform after the value of V2 is V1 after voltage decline.
4. lithium ion battery B ohmic internal resistance of table
Table 5. lists in the case that charging current is 1C, 2C, 4C, 6C respectively, and the method measurement is simultaneously through the invention
The electric charge transfer internal resistance value (Rct) for the lithium ion battery B being calculated is calculated according to formula Rct=(V2-V3)/I, and V3's takes
Value point is determined by following formula, i.e., when voltage is less than preset value C1 relative to the ratio between changing value of time and the moment voltage value
Point: | dV/dt |/V < C1, the value of C1 is 0.05s in the embodiment-1。
5. lithium ion battery B electric charge transfer internal resistance of table
Table 6. lists in the case that charging current is 1C, 2C, 4C, 6C respectively, and the method measurement is simultaneously through the invention
The diffusion internal resistance value (Rd) for the lithium ion battery B being calculated, calculates according to formula Rd=(V3-V4)/I, and the data point of V4 is
Cell voltage reach steady after voltage value.
6. lithium ion battery B of table spreads internal resistance
Embodiment 3
In the present embodiment using to key instrument equipment include computer, a Tai Xinwei cell tester (CT-4004-
5V300A-NTFA), for carrying out charge and discharge, the voltage of a high-speed data acquisition instrument detection battery to battery, other equipment are
Common accessory.
Measurement object is lithium ion battery C in the present embodiment, and just extremely trielement composite material, cathode are porous carbon
Material, marked capacity 10Ah are comprised the steps that
1. lithium ion battery C is connect with measuring device according to Fig. 1.
2. the temperature that lithium ion battery C is placed in insulating box, and controls lithium ion battery C is -10 DEG C.
3. its SOC is adjusted to 50% according to the marked capacity of lithium ion battery C and reaches balance (in charging and discharging currents section
It is considered that reaching balance after standing at least 1 hour after only).
4. adjustment lithium ion battery C temperature reaches -10 DEG C.
5. using 1C electric current to lithium ion battery C electric discharge 10s, while using cell tester and high-speed data acquisition instrument
(time step is set as 10 microseconds) recording voltage data.
6. standing 1 hour.
7. its SOC is adjusted to 50% according to the marked capacity of lithium ion battery C and reaches balance (in charging and discharging currents section
It is considered that reaching balance after standing at least 1 hour after only).
8. repeating step 4 to 7 (discharge current need to be changed to 1.5C, 2C, 2.5C and 3C in steps of 5) until completing all
Test.
The lithium ion that the method is measured and is calculated through the invention under table 7. lists discharge current from 1C to 3C
The ohmic internal resistance value (Ro) of battery C is calculated according to formula Ro=(V2-V1)/I, detects the battery electricity of battery discharge cut-off time
Pressure value is V1, the platform voltage of first platform after the value of V2 is V1 after voltage recovery.
7. lithium ion battery C ohmic internal resistance of table
Table 8. list discharge current respectively from 1C to 3C under the method is measured and is calculated through the invention lithium
The electric charge transfer internal resistance value (Rct) of ion battery C is calculated according to formula Rct=(V3-V2)/I, and the data point of V3 is by following public affairs
Formula is determining, i.e. the point when voltage is less than preset value C1 relative to the ratio between changing value of time and the moment voltage value: | dV/dt
|/V < C1, the value of C1 is 0.025s in the present embodiment-1。
8. lithium ion battery C electric charge transfer internal resistance of table
The lithium ion that the method is measured and is calculated through the invention under table 9. lists discharge current from 1C to 3C
The diffusion internal resistance value (Rd) of battery C is calculated according to formula Rd=(V4-V3)/I, and the data point of V4 is that cell voltage reaches steady
Voltage value afterwards.
9. lithium ion battery C of table spreads internal resistance
Embodiment 4
In the present embodiment using to key instrument equipment include computer, a Tai Xinwei cell tester (CT-4004-
5V300A-NTFA), for carrying out charge and discharge, the voltage of a high-speed data acquisition instrument detection battery to battery, other equipment are
Common accessory.
Measurement object is lithium ion battery D in the present embodiment, and just extremely trielement composite material, cathode are porous carbon
Material, marked capacity 10Ah are comprised the steps that
1. lithium ion battery D is connect with measuring device according to Fig. 1.
2. the temperature that lithium ion battery D is placed in insulating box, and controls lithium ion battery D is 55 DEG C.
3. its SOC is adjusted to 50% according to the marked capacity of lithium ion battery D and reaches balance (in charging and discharging currents section
It is considered that reaching balance after standing at least 1 hour after only).
4. adjustment lithium ion battery D temperature reaches 55 DEG C.
5. using 1C electric current to lithium ion battery D electric discharge 10s, while using cell tester and high-speed data acquisition instrument
(time step is set as 10 microseconds) recording voltage data.
6. standing 1 hour.
7. its SOC is adjusted to 50% according to the marked capacity of lithium ion battery D and reaches balance (in charging and discharging currents section
It is considered that reaching balance after standing at least 1 hour after only).
8. repeating step 4 to 7 (discharge current need to be changed to 2C, 4C, 6C, 8C and 10C in steps of 5) until completing all
Test.
Table 10. list discharge current from 1C to 10C under through the invention the method measure and the lithium that is calculated from
The ohmic internal resistance value (Ro) of sub- battery D is calculated according to formula Ro=(V2-V1)/I, detects the battery of battery discharge cut-off time
Voltage value is V1, the platform voltage of first platform after the value of V2 is V1 after voltage recovery.
10. lithium ion battery D ohmic internal resistance of table
Table 11. list discharge current respectively from 1C to 10C under through the invention the method measure and be calculated
The electric charge transfer internal resistance value (Rct) of lithium ion battery D is calculated according to formula Rct=(V3-V2)/I, and the data point of V3 is by following
Formula is determining, i.e. the point when voltage is less than preset value C1 relative to the ratio between changing value of time and the moment voltage value: | dV/
Dt |/V < C1, the value of C1 is 0.05s in the present embodiment-1。
11. lithium ion battery D electric charge transfer internal resistance of table
Table 12. list discharge current from 1C to 10C under through the invention the method measure and the lithium that is calculated from
The diffusion internal resistance value (Rd) of sub- battery D is calculated according to formula Rd=(V4-V3)/I, and the data point of V4 is that cell voltage reaches flat
Voltage value after steady.
12. lithium ion battery D of table spreads internal resistance
Embodiment 5
In the present embodiment using to key instrument equipment include computer, a Tai Xinwei cell tester (CT-4004-
5V300A-NTFA), for carrying out charge and discharge, the voltage of a high-speed data acquisition instrument detection battery to battery, other equipment are
Common accessory.
Measurement object is lithium ion battery E in the present embodiment, and just extremely trielement composite material, cathode are porous carbon
Material, marked capacity 10Ah are comprised the steps that
1. lithium ion battery E is connect with measuring device according to Fig. 1.
2. the temperature that lithium ion battery E is placed in thermostatic chamber, and controls lithium ion battery E is 25 DEG C.
3. its SOC is adjusted to 25% according to the marked capacity of lithium ion battery E and reaches balance (in charging and discharging currents section
It is considered that reaching balance after standing at least 1 hour after only).
4. adjustment lithium ion battery E temperature reaches 25 DEG C.
5. using 1C electric current to lithium ion battery E electric discharge 10s, while using cell tester and high-speed data acquisition instrument
(time step is set as 10 microseconds) recording voltage data.
6. standing 1 hour.
7. its SOC is adjusted to 25% according to the marked capacity of lithium ion battery E and reaches balance (in charging and discharging currents section
It is considered that reaching balance after standing at least 1 hour after only).
8. repeating step 4 to 7 (discharge current need to be changed to 2C, 3C, 4C, 5C and 6C in steps of 5) until completing all
Test.
The lithium ion that the method is measured and is calculated through the invention under table 13. lists discharge current from 1C to 6C
The ohmic internal resistance value (Ro) of battery E is calculated according to formula Ro=(V2-V1)/I, detects the battery electricity of battery discharge cut-off time
Pressure value is V1, the platform voltage of first platform after the value of V2 is V1 after voltage recovery.
13. lithium ion battery E ohmic internal resistance of table
Table 14. list discharge current respectively from 1C to 6C under the method is measured and is calculated through the invention lithium
The electric charge transfer internal resistance value (Rct) of ion battery E is calculated according to formula Rct=(V3-V2)/I, and the data point of V3 is by following public affairs
Formula is determining, i.e. the point when voltage is less than preset value C1 relative to the ratio between changing value of time and the moment voltage value: | dV/dt
|/V < C1, the value of C1 is 0.05s in the present embodiment-1。
14. lithium ion battery E electric charge transfer internal resistance of table
The lithium ion that the method is measured and is calculated through the invention under table 15. lists discharge current from 1C to 6C
The diffusion internal resistance value (Rd) of battery E is calculated according to formula Rd=(V4-V3)/I, and the data point of V4 is that cell voltage reaches steady
Voltage value afterwards.
15. lithium ion battery E of table spreads internal resistance
Embodiment 6
In the present embodiment using to key instrument equipment include computer, a Tai Xinwei cell tester (CT-4004-
5V300A-NTFA), for carrying out charge and discharge, the voltage of a high-speed data acquisition instrument detection battery to battery, other equipment are
Common accessory.
Measurement object is lithium ion battery F in the present embodiment, and just extremely trielement composite material, cathode are porous carbon
Material, marked capacity 10Ah are comprised the steps that
1. lithium ion battery F is connect with measuring device according to Fig. 1.
2. the temperature that lithium ion battery F is placed in thermostatic chamber, and controls lithium ion battery F is 25 DEG C.
3. its SOC is adjusted to 95% according to the marked capacity of lithium ion battery F and reaches balance (in charging and discharging currents section
It is considered that reaching balance after standing at least 1 hour after only).
4. adjustment lithium ion battery F temperature reaches 25 DEG C.
5. using 1C electric current to lithium ion battery F electric discharge 30s, while using cell tester and high-speed data acquisition instrument
(time step is set as 10 microseconds) recording voltage data.
6. standing 1 hour.
7. its SOC is adjusted to 95% according to the marked capacity of lithium ion battery F and reaches balance (in charging and discharging currents section
It is considered that reaching balance after standing at least 1 hour after only).
8. repeating step 4 to 7 (discharge current need to be changed to 2C, 4C, 6C, 8C and 10C in steps of 5) until completing all
Test.
Table 16. list discharge current from 1C to 10C under through the invention the method measure and the lithium that is calculated from
The ohmic internal resistance value (Ro) of sub- battery F is calculated according to formula Ro=(V2-V1)/I, detects the battery of battery discharge cut-off time
Voltage value is V1, the platform voltage of first platform after the value of V2 is V1 after voltage recovery.
16. lithium ion battery F ohmic internal resistance of table
Table 17. list discharge current respectively from 1C to 10C under through the invention the method measure and be calculated
The electric charge transfer internal resistance value (Rct) of lithium ion battery F is calculated according to formula Rct=(V3-V2)/I, and the data point of V3 is by following
Formula is determining, i.e. the point when voltage is less than preset value C1 relative to the ratio between changing value of time and the moment voltage value: | dV/
Dt |/V < C1, the value of C1 is 0.05s in the present embodiment-1。
17. lithium ion battery F electric charge transfer internal resistance of table
Table 18. list discharge current from 1C to 10C under through the invention the method measure and the lithium that is calculated from
The diffusion internal resistance value (Rd) of sub- battery F is calculated according to formula Rd=(V4-V3)/I, and the data point of V4 is that cell voltage reaches flat
Voltage value after steady.
18. lithium ion battery F of table spreads internal resistance
It is shown from above-mentioned measurement result, method proposed by the present invention can measure the charge and discharge that battery allows in any design
Electric current and three kinds of not same polarizations (i.e. ohmic polarization, activation polarization and concentration polarization) after the charge and discharge time and corresponding
Internal resistance.It is also seen that electrochemical overpotential | V3-V2 | and concentration overvoltage | V4-V3 | it is nonlinear dependence between electric current
System is in particular in that electric charge transfer internal resistance and diffusion internal resistance are changed with curent change.This also illustrates to survey using EIS method
The electric charge transfer internal resistance obtained can not represent electric charge transfer internal resistance of the battery core under real work electric current.This has also fully demonstrated this hair
Bright importance and practicability.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
In the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Subject to enclosing.
Claims (15)
1. a kind of measurement method of the internal resistance of cell characterized by comprising
A. battery is provided, control battery temperature reaches test temperature；
B. using predetermined current I to battery carry out constant-current discharge or charging one preset time after end, record from electric discharge or
Cell voltage of the charge cutoff moment to voltage when steady；
It detects battery discharge or the battery voltage value at charge cutoff moment is V1, the battery voltage value after ohm overpotential disappears is
V2,
C. according to formula Ro=| V2-V1 |/I calculates ohmic internal resistance Ro.
2. a kind of measurement method of the internal resistance of cell characterized by comprising
A. battery is provided, control battery temperature reaches test temperature；
B. using predetermined current I to battery carry out constant-current discharge or charging one preset time after end, record from electric discharge or
Cell voltage of the charge cutoff moment to voltage when steady；
Detecting the battery voltage value after ohm overpotential disappears is V2, the battery after ohm overpotential and the disappearance of electrochemistry overpotential
Voltage value is V3,
C. according to formula Rct=| V3-V2 |/I calculated charge shifts internal resistance.
3. a kind of measurement method of the internal resistance of cell characterized by comprising
A. battery is provided, control battery temperature reaches test temperature；
B. using predetermined current I to battery carry out constant-current discharge or charging one preset time after end, record from electric discharge or
Cell voltage of the charge cutoff moment to voltage when steady；
Battery voltage value after detecting ohm overpotential and the disappearance of electrochemistry overpotential is V3, and ohm overpotential, electrochemistry are excessively electric
Battery voltage value after position and concentration overpotential all disappear is V4,
C. according to formula Rd=| V4-V3 |/I calculates diffusion internal resistance.
4. the measurement method of the internal resistance of cell according to claim 1 or 2, which is characterized in that the value of the V2 be V1 it
Afterwards voltage recovery or fall after rise after first platform platform voltage.
5. the measurement method of the internal resistance of cell according to claim 2 or 3, which is characterized in that the data point of the V3 by with
Lower formula determines, i.e., after V2 when voltage relative to the ratio between changing value of time and the moment voltage value less than preset value C1 when
Point: | dV/dt |/V < C1.
6. the measurement method of the internal resistance of cell according to claim 5, which is characterized in that the value of the C1 is in 0.001s-1
To 0.5s-1Between.
7. the measurement method of the internal resistance of cell according to claim 6, which is characterized in that the value of the C1 is in 0.01s-1Extremely
0.2s-1Between.
8. the measurement method of the internal resistance of cell according to claim 3, which is characterized in that the value of the V4 is cell voltage
Voltage value after reaching steady.
9. the measurement method of the internal resistance of cell according to any one of claims 1 to 3, which is characterized in that provide battery, the electricity
The SOC in pond is between 0% to 100%.
10. the measurement method of the internal resistance of cell according to any one of claims 1 to 3, which is characterized in that the predetermined current I
Any value selected from 0.1C into 30C.
11. the measurement method of the internal resistance of cell according to any one of claims 1 to 3, which is characterized in that described preset fills constant current
Any value of the charge and discharge time in 0.01 second to 10 hours.
12. the measurement method of the internal resistance of cell according to claim 11, which is characterized in that described preset fills constant current charge-discharge
Any value of the time in 1 second to 300 seconds.
13. the measurement method of the internal resistance of cell according to any one of claims 1 to 3, which is characterized in that adopted using high-speed data
Collect instrument and detects the cell voltage.
14. the measurement method of the internal resistance of cell according to claim 13, which is characterized in that the high-speed data acquisition instrument
Data acquisition time step-length is selected from any value of 0.1 microsecond to 1 second.
15. the measurement method of the internal resistance of cell according to claim 14, which is characterized in that the high-speed data acquisition instrument
Data acquisition time step-length is selected from any value of 1 microsecond to 1 millisecond.
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| US16/177,355 US10921380B2 (en) | 2017-11-01 | 2018-10-31 | Method for measuring the internal resistance of batteries |
| EP18203829.9A EP3480613B1 (en) | 2017-11-01 | 2018-10-31 | Method for measuring the internal resistance of batteries |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP3480613B1 (en) | 2023-09-06 |
| US20190128969A1 (en) | 2019-05-02 |
| US10921380B2 (en) | 2021-02-16 |
| EP3480613A1 (en) | 2019-05-08 |
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Application publication date: 20190514 |